Process fob modifying fatty oils



?atented Mar. 19,1945

rnocass FOR Laszlo Auer, South Orange, N. J.

No Drawing; Application October 12, 1942,

Serial No. 461,789 a 23 Claims.

GENERAL FIELD OF INVENTION AND STATEMENT OF OBmcrs Th is invention relates to the modification of fatty oils. The present application is a continuation-in-part of my copending application Serial No. 383,339 filed March 14, 1941, now Patent No. 2,298,915 issued October 13, 1942..

Fatty oils are employed in a number of difierent industries, such, fo instance, as the coatings and plastics industries, and it is a general object of this invention to modify and improve the properties of fatty oils for variou industrial purposes.

Briefly. the invention contemplates treatment of a fatty oil, for instance linseed oil, with fiuorescein, with application of heat. Full description of the treatment hereinafter.

According to the present invention it is possibl to achieve a number of advantages in the treatment of fatty oils. For example, it is po sible to materially accelerate the rate of bodying of a fatty oil. It is further possible to materially improve the drying characteristics of the fatty oil, and also to improve water and alkali resistance of film coatings or the like formed with the treated oil. Still further, the treatment yields a modified oil which has special advantages in the field of electrical insulation, since the modified oil yields coatings having increased dielectric strength.

The foregoing and other objects andadvantages will be considered more fully hereinafter following a description of two illustrative processes. However, before proceeding with the description, reference is now made to the fatty oil materials to which the invention is applicable.

FATTY OIL The process may be employed on fatty oils generally, including drying oils, semi-drying oils, and non-drying Oils. The following is a typical list of such oils.

Tung oil Oiticica oil Dehydrated castor oil Linseed oil Perilla oil Sunflower oil Poppyseed oil Soya bean oil Walnut 011. Rapeseed oil Pine seed oil procedure is given Olive oil Corn oil Cottonseed oil Coconut oil Babassu oil Hydroxylated oils such ascastor oil, etc.- Fish oils (train oils) in which event the fiuorescein may conveniently be added at the time of cooking the varnish, so that the several ingredients of the varnish solids. are, so to speak, Jointly treated or modified.

, 2 Fmsr ILLUSTRATIVE Paocass A batch of. linseed oil is heated together with 2% of fiuore'sceinthe temperature being maintained at about 30010. for 5 hours. Vacuum is applied during the treatment period and the pres- I sure maintained at about 100 mms. Hg.

The modified oil is a heavily bodied oil of an orange color, having a very strong fluorescence. A varnish made with the treated oil has an 4 unusually strong gel skeleton, which results in improved drying properties, especially in the initial drying stage, so that the varnish reaches the print-free" stage veryvquickly. In addition the resistance to hot water and alkali of a varnish made with the treated oil is unusually good,'cold water, resistance also being at least equivalent to a varnish made with the same oil heated under the same conditions but without the fluorescein.

Varnish film made with the. treated oil display a markedly improved dielectric strength.

Sacorm ILLUSTRATIVE Pnocass Various of the foregoing improvements are also obtainable by employment of an alternative process wherein, the fiuorescein is made in situ, i. e.,

by treating the oil with resorcinol and phthalic anhydride added as such. In the case of this.

treatment, the resorcinol andphthalic anhydride are desirably added in those chemical proportions which are capable of combining to form the fluore'scein. The molecular proportion of the two ingredients is two molecules of resorcinol for each one molecule of phthalic anhydride. To achieve used. I

this molecular proportion, the weight proportion should be about two parts of phthalic anhydride to three parts of resorcinol. Y

As the second illustrative process, therefore, a batch of linseed oil is-treated with .2% of phthalic anhydride and 3% of resorcinol, the mixture being heated to about 300 C. under a pressure of 100 me. Hg' for a period of 5 hours.

Although the bodying rate is not increased to the same extent as when employing pre-condensed fluorescein, the oil treated with phthalic anhydride and resorcinol displays similarly improved drying properties and water and alkali resistance.

In addition, when forming the fiuorescein in situ the color of the modified oil-is very excellent for many purposes, being very light in color, and not displaying the distinctive orange shade characteristic of treatment with. pro-condensed fiuorescein.

Improved dielectric strength is also noted in varnish films made with oil treated with phthalic anhydride and resorcinol.

A number of variations may be introduced in etiher of the foregoing illustrative processes, these variations being mentioned more fully hereinafter following the specific examples which are given just below.

In considering the following examples, and in other discussion in the present specification, it

asoaovo is to be understood that statements regarding changes in properties and comparisons thereof are always made on the basis of a relation between the product treated with the modifying agent-and a product treated in exactly the same manner (heating, etc.) but without a modifying agent. The latter is often herein referred to as a blank" or control experiment.

Temperatures are always given in degrees centigrade, and viscosities are identified on the Gardner scale, unless otherwise specified. All parts mentioned are .by weight.

EXAMPLES Several comparative series of experiments were conducted in order to demonstrate the efiect of varying the proportion of modifying agent. In one such comparative series, presented in Table I herebelow, a batch of 300 gms. of alkali refined linseed oil was heated in a 1 liter aluminum beaker, and a blanket of CO2 gas maintained over the surface of the batch. In this series prefor 1 hour. The mixture was cooled to 200 C.

and diluted with mineral spirits to 50% solids. Naphthenate driers were added in the proportion of .03% cobalt metal, .02% manganese metal and .30% lead metal, based on the quantity of oil The varnishes were tested for drying, cold water resistance, hot water resistance, and alkali resistance.

A blank experiment on the same alkali refined linseed oil was also conducted under exactly the same treatment conditions (temperature, etc.)

but without the fluorescein; and a varnish was prepared from this blank."

The results of the several experiments of the series and of the "blank" are indicated in the following table:

Table I .Flu0rescein press relation to the blank.

The testing of the varnishes was done in the following manner:

Varnish film were applied to steel panels by means of a coating knife yielding a film .003 of an inch thick. The drying of the varnishes on the panels was observed both with respect to initial drying (in the first 5 hours), and also after overnight drying. After the panels had been left for 48 hours to insure through-drying, the panels were tested for cold 'water resistance, boiling water resistance and alkali resistance.

' The test for cold water resistance was conducted by immersing one-half of each panel in cold water for 24 hours, and then observing the appearance of the films.

The test for boiling water resistance was effected by immersing one-half of each panel in boiling water for 15 minutes, .and then observing the appearance of the films, particularly for milkiness and softness, but also for the speed with which the milky films returned to their original appearance upon drying in the air.

The test for alkali resistance was effected by immersing one-half of each panel in 3% sodium hydroxide solution, and observing the time when the alkali completely attacked and dissolved the films.

A similar series of experiments was conducted in the same general manner, except that the batch undergoing treatment was heated in a 1.

liter distilling flask at a pressure of mms.-Hg

instead of employing a C02 blanket. The results of this series are indicated in Table II just below: Table IL-illuorescein A batch of 300 gms. of dehydrated castor oil was heated, together with .05% fiuorescein, in a distilling flask, the temperature being maintained at about 300 C. for a period of one and one-half hours. The oil was of quite light color and reached a viscosity of Z6. A 25 gallon long varnish was prepared in the manner described above and when diluted to 50% solids reached a viscosity of G. The varnish had good drying properties and good resistance to both hot and cold. water, and in addition the varnish displayed excellent alkali resistance, the film still beingintact after 24 hours immersion in the 3% sodium hydroxide solution.

. Example 10 A similar experiment was conducted with dehydrated castor oil, employing. 5% fiuorescein. With this percentage, the mixture was heated for 46 minutes atv 300 C., at'the end of which time the viscosity was Z6++. The color of the oil wassomewhat darker than that of Example 9.

A similar varnish was prepared in the manner outlined above, employing the oil of Example 10 and this varnish displayed good drying properties, as well as hot and cold water and alkali resistance.

Dehydrated castor oil with fiuorescein shows very rapid bodying, if heavy bodied oils are being made. If a varnish is cooked out of such oils, the varnish bodying speed is also accelerated.

Example 11 A batch of 300 gms. of alkali refined linseed oil was heated in an open 1 liter aluminum beaker together with .5% fiuorescein for 5 hours between about 295 C. and 305 C. A similar batch of oil On starting the next day, the oil'was noticed to be. quite thick, but it quickly thinned on reheating, requiring about three-quarters of an hourto again reach 290 C. The batch was then kept betweenabout 290 C. and 302 C. for an additional three and oneequarter hours, so that the entire timeon temperaturetotaled five hours. The product. when cooled, was a brown elastic jell with a strong green fluorescence.

gallon long varnishes weremade with the oils of Examples 12 and 13 and in addition similar varnishes were made, with the same oils treated in the same manner except for the omissionof the modifying agent. The varnishes were made with lime hardened rosin. The varnishes were initially tested without driers, and both of the varnishes made with fiuoresceintreated oils reached the final drying stage much without the fiuorescein was treated inthe same manner, as a blank experiment. The-following tabulation indicates the comparative results secured with the blank (C) and with the fluorescein treated oil. The varnish was prepared in the same manner as that described above.

more quickly than the two corresponding blank varnishes. Upon addition of cobalt drier to the varnishes, the varnish made with the product of Example 13 dried much faster than the corre- Table III.Fluorescein A batch of linseed oil was heated in a distilling flask with 5% of fiuorescein under a pressure of about mms. Hg. During initial heating there was a sudden rise in temperature from about 80 C. to about 160 C., accompanied by frothing, which, however, subsided at about 200 C. when some gas evolution occurred. Fifty minutes was Example 13 A batch of linseed oil (pro-dried of moisture content) was heated in an open iron beaker with 5% of fiuorescein. About one and three-quarter hours was required to reach 290 C. The mixture was then kept between about 290 C. and 302 C. for one and three-quarter hours, and then permitted to cool overnight.

The oil The varnish 4 Rx. No. Drying properties C Viscos Color of Vise. of 3: 35. Hot water Alkali o y varnish varnish r t e resistance resistance Initial Overnight ll 13 Z-3 15 A VG VG VG VG Qvernight. C 10 Z-2 12 A- F F F B 5% hours.

Key to chart:

Colors in Hellige comparator sca1e VG-very good.

F-feir. B-bad.

Example 12 In each example 169 parts of alkali refined linseed oil and 20' parts of a modified phenolic resin (rosin modified) were initially heated to 300 C. together with the fiuorescein and held at that temperature for two and three-quarter hours. 30 parts of lime hardened rosin were then added and the mixture reheated to 300 C. and held there for ten minutes. 10 parts of zinc resinate were added. Following the zinc resinate addition the batch was again reheated to 300 C. and

held for one-half hour. Then driers were also pared in essentially the same manner as that described above except tofomisSion of the iluoq Example 17 Batches of 5,000 gms. of alkali refined linseed reseein, H oil were heated in aluminum pots under CO2 "Table rv.-Fluorescein A Drying Dielectric Volts Heat Oil 1%. :53??? e 635 ge ag p g no C. Y hours "Q55,

14 0. 888 1-1 2% l, 585 405 408 378 886 F 2 l. 820 640 408 250 D..- .884 F-G 1% 1,385 330 312 300 All of the tests indicated in the above table were made in accordance with A. S. T. M. methods. In addition it may be noted that while the blank" had a rating (A. S. T. M.) of 51, the varnish of Example-14 had a rating of 52 and that of Example 15 had a rating of 60.

Example 16 Table V.--Fluorescein blanket, the temperature being 300 C. The following percentages were used, some with, and some without mechanical agitation, as indicated. All batches were heated until the oil reached a body of from Z5 to Z6.

.05% of the reagent mixture was used with agitation.

05% of the reagent mixture was used without agitation.

(c) .l% was used without agitation.

(d) .5% was used without agitation.

(e) 2% was used with agitation.

(f) 5% was used with agitation.

(g) A "blank experiment was also conducted without agitation.

Example 18 A similar group of experiments was conducted on batches of 8,000 gms. of alkali refined linseed oil heated in a 22-liter distilling flask under vac Drying Dil m v its on Ex. Specific Vise time ig c o endurance gtb per mil resistance gravity 3 5 dry 1 wet Sig hardness i6---.. 0.890 R 54 1,870 775 Over 1,000 500 E 882 A- X 1, 770 545 Over 1, 0) 375 Tack.

The varnish of Example 16 indicated a rating of 80+, which compared with 60+ for the "blank" Note the high viscosity of the varnish 16 with fluorescein and the extremely low viscosity of the corresponding blank E. The foregoing tables indicate that employment of fluorescein in insulating varnishes increases to a great extent the dielectric strength, both when wet and when dry, the varnishes employing fluorescein also yielding quite rapid baking time, long life and fair oil resistance. Comparison of the two sets of experiments (on insulating varnishes) further show that substitution of ester gum for the lime hardened rosin and zinc resinate further improve the qualities of the varnish.

In order, to demonstrate the efiect of treating a fatty oil with phthalic anhydride and resorcinol, so as to iorm the fluorescein in situ. some additional comparative experiments were conducted, these being treated of under Examples 17 and 18 below. In all experiments of these two series the phthallc anhydride and resorcincl were used in relative proportions of 2 to 3 by weight. In the discussion just below it is to be understood that the percentage of reagent given indicates the totalpercentage of the two ingredients in the proportions just mentioned.

very light color.

uum (pressure 100 inms. Hg). Here again the temperature was 300 C. and the oils were heated until a body of Z5 to Z6 was attained.

(a) 45% was used with agitation.

(b) .5% was used without agitation.

(c) A blank experiment was conducted without agitation.

Although the rate of bodying of the oil in general, was only slightly accelerated in the two examples just above noted, it is of importance to note that theoil products were consistently of nishes with the above oils it is of importance to note that the time required to cook the varnish to a given body (varnish bodying time) was materially decreased by the employment of the oils treated with phthalic anhydride and resorcinol. Especially fast bodying of the varnish was shown in the varnishes made up as indicated under (a) and (d) of Example 17 and (a) of rescein is from about ;.05% to about Example 18. Improvement in varnish bodying time was as much as 20 to 30%.

With respect to drying of these varnishes, it may be noted that they indicated somewhat faster initial drying, and in many cases very definitely improved through-drying in an overnight period. This is especially true of items (a), (b), (e) and (1") of Example 17 and also of items (a) and (b) of Example 18.

Cold and boiling water resistance tests indicated results at least equivalent to the blank experiments. The alkali resistance of the varnishes prepared with the oils treated with the reagent mixture was consistently better than the blank, although the improvement in this respect is not as notable as where the fiuorescein is used in pre-condensed form.

RANGES AND VARIATIONS OF TREATMENT In addition to the examples given above, it has been demonstrated by other actual examples that effective results are secured by first preparing a master batch of a fatty oil containing a relatively high percentage of phthalic anhydride and resorcinol, and thereafter diluting a relatively large batch of fatty oil with the master batch. This has the advantage of enabling the preparation of relatively large quantities of oil in relatively small equipment, since only the master batch need be specially handled. In one instance master batches containing 20% of phthalic anhydride and. resorcinol (in the relative proportions of .2 to 3) were prepared by heating only until the When using phthalic anhydride-resorcinoi mixtures the reagent may be employed up to or even although an effective range is from about .05% to about 10%. 1

The time will vary depending upon the other conditions of the process, such as percentage, temperature, etc., and also upon whether or not the fiuorescein is employed in pre-condensed form or is formed in situ. Note for instance that to achieve a given body when treating an oil, greater time is required when forming the fiuorescein in situ than when employing pre-condensed fiuorescein. In the latter case, in fact, extremely rapid bodying is obtainable. As a gen-'- eral guide it may be saidthat a few hours, for

instance from about 1 hour to about 5 or 10 hours is sufiicient, With certain oils, and under certain conditions (note for instance Examples 9 and '10, above, using dehydrated castor oil), extensive bodying takes place even in a matter of minutes.

The treatment may be carried out under varying atmospheric conditions, both with respect to pressure and also with respect to the gas in contact withthe reaction mixture. Thus, in examples given above, certain oils were treated under vacuum and others at atmospheric pressure. Moreover, some of the examples employed a blanket of CO2. j

It is frequently of advantage to exclude the air from a reaction mixture and this may be done either by employing vacuum or by blanke'ting the I surface 'of the batch with some inert gas, for inpors or the like released from the reaction mass may serve to dispel or exclude the air. I have found vacuum treatment to be particularly effective, for instance from about 100 mms. Hg to about 450 mm Hg, although higher or lower pres- In connection with the modifying agent it may" be mentioned that substituted fluorescein, its derivatives and salts may also be used. Moreover, in the alternative process (preparation ofv the modifying agent in situ) materials may be used which yield either fiuorescein itself, or substituted fiuorescein, its derivatives and salts.

With respect to variations of temperature, etc., note the following:

The temperature in treating an oil with fluorescein may be anywhere from about 200 C. up

to about 350 0., preferably not above the point at which the oil boils or decomposes. An effective range has been found tube from about 250 C. to about 310 C. 7

When using phthalic anhydride-resorcinol mixtures, a master batch may be mixed into oils even cold, andsuch oils may'react with the a ents either while bodying oils and/or while cooking varnishes with such oilsv V Although under at least some circumstances. the modifying agent may be employed in a relatively high percentage, for instance up to about 30%, when using fluorescein the quantity should not. usually be above about 10%, especially because of the fact that the fiuorescein is diflicultly soluble in fatty oils. An effective range for fluo- However, in the event of usingv certain auxiliary agents or resins (such as are used in varnish 'cooking), dissolution of the fiuorescein may be promoted, in which event more than 10% may be employed.

sures are also useable.

1 With regard to the foregoing atmospheric conapplied to the oil, either during or following the ditions in the reaction vessel, it maybe noted that certain of the gases mentioned may be employed for their supplemental effect on the reaction, in

which event, if desired, the gases may be bubbled through the reaction mixture.

In general it may be pointed out that increasing any one of the temperature, rme or percentage of modifying agent usually increases the rate and/or extent of the reaction.

The modifying agent herein claimed may be employed (either simultaneously or sequentially) in combination with others disclosed, for instance, in various of my copending applications and is-.

sued patents, some of which are mentioned hereinafter. Interesting results may be obtained for instance when oils made according to my copendreaction with fluorescein. many of such supplemental-treatments also being discussed fully in copending applicationsand issued patents below mentioned. For instance, the modified oil products may be vulcanized with sulphur or sulphur chlorid or similar vulcanizing agents.

Particularly effective results are secured with a vulcanized oil product, where the oil has been treated with fluorescein or with phthalic anhytion is a continuation-in-part of m copending application Serial No. 383,339 now Patent No. 2,293,915 issued October 13, 1942. Certain subject matter disclosed herein is also disclosed in my copending application Serial No. 318,650 filed February 12, 1940 now Patent No. 2,298,270 issued October 13, 1942, and also in application Serial No. 359.425 (now patent No. 2,213,944). Application 446,170 (now Patent 2,234,949), of which Serial No. 318,650 is a continuation-in-part, also presents similar subject matter.

- I claim:

1. The method of modifying a, fatty oil to improve its drying characteristics which comprises incorporating in the oil up to 30% of iiuorescein and heating the mixture to a temperature between about 200 C. and about 350 C. but not above the boiling point of the oil.

2. The method of modifying a fatty oil to improve its drying characteristics which comprises incorporating in the oil up to 10% of fiuorescein, and heating the mixture to a temperature between about 200 C. and 350 C. but not above the boiling point of the oil.

3. A process in accordance with claim 2 in which the fluorescein is present in an amount from about .05% to about 5%.

anhydride and 'resoroinol in a master batch of fatty oil, and thereafter combining oil of said master batch with a larger quantity of fatty oil, and heating the resulting mixture to heat bodying temperatures, the phthalic anhydride and resorcinol being employed in proportions in which they combine chemically with each other.

14. A heat bodied fatty oil product having dispersed therein the reaction product of up to 10% of fluorescein with the fatty oil, the quantity of the reacted fluorescein being based on the heat bodied fatty 011 product.

15. The method of modifying a fatty oil which Q comprises dispersing in the'oil up to 30% of a 4. The method of modifying a fatty oil to improve its drying characteristics which comprises incorporating in the oil up to 30% of a modifying agent comprising phthalic anhydride and resorcinol, and heating the mixture to a temperature between about 200 C. and 350"v C. but not above the boiling point of the oil, the phthalic anhydride and resorcinol being employed in proportion in which they combine chemically with each other.

5. A process in accordance with claim 1 in which the quantity of the flourescein is from about 05% to about 10%.

6. A process in accordance with claim 1 in which the fatty oil is linseed oil.

7. A process in accordance with claim 1 in which the fatty oil is soya bean oil.

8. A process in accordance with claim 1 in from about .05% to about 5%.

13. A process for treating fatty oils which comprises'flrst dispersing a relatively high percentage of a modifying agent comprising phthalic modifying agent comprising phthalic anhydride and resorcinol, heating the oil, subsequent to dispersion of the modifying agent, to a temperature between about 200 C. and 350 C., the phthalic anhydride and resorcinol being employed in proportions in which they combine chemically with each other.

16. The process of claim 1, in which the modified fatty oil is heated with sulfur to form a vulcanized fatty oil product.

1'7. A heat bodied fatty oil material comprising the reaction product of fiuorescein formed with the fatty oil, the quantity of the reacted fluorescein being up to 30% of the heat bodied fatty oil material.

18. A vulcanized heat bodied fatty oil material comprising the reaction product of fluorescein formed with the fatty oil, the quantity of the reacted fiuorescein being up to 30% of the heat bodied fatty oil material.

19. A heat bodied fatty oil material comprising the reaction product of phthalic anhydride and resorcinol formed with the fatty oil, the quantity of the reacted phthalic anhydride and resorcinol being up to 30% of the heat bodied fatty'oil material.

20. A vulcanized heat bodied fatty oil material comprising the reaction product of phthalic an-v hydride and resorcinol formed with the fatty oil, the quantity of the reacted phthalic anhydride and resorcinol being up to 30 of the heat bodied fatty oil material.

' 21. The process in accordance with claim 1 in which the iiuorescein is formed in situ under the conditions of the treatment from phthalic anhydride in admixture with resorcinol.

22. A heat bodied fatty oil material comprising the reaction product of phthalic anhydride and resorcinol formed with the fatty oil, the quantity of the reacted phthalic anhydride and resorcinol 

